CN108550702A - Translucent organic solar batteries and its preparation method and the application in photovoltaic agricultural greenhouse - Google Patents
Translucent organic solar batteries and its preparation method and the application in photovoltaic agricultural greenhouse Download PDFInfo
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- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
- H10K30/211—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
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- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
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Abstract
The invention discloses a kind of translucent organic solar batteries can be applied to photovoltaic agricultural greenhouse and preparation method thereof and its application in photovoltaic agricultural greenhouse.Active layer in the translucent organic solar batteries is to serve as donor, non-fullerene small molecule IEICO 4F and fullerene PC based on organic polymer 5271BM serves as the binary or ternary system of receptor, the organic polymer J52, non-fullerene small molecule IEICO 4F, fullerene PC71The mass ratio of BM is 1:(0~1.5):(0~1.5), the active layer thickness are 90~100nm.The active layer of the solar cell is to absorb stronger organic material in infrared and near infrared band.By making visible light-transmissives more as possible, non-visible light are absorbed and utilized by reflection and then by active layer, to improve the mean transmissivity and energy conversion efficiency of device simultaneously.
Description
Technical field
The invention belongs to organic electro-optic device technical fields, and in particular to a kind of to can be applied to the semi-transparent of photovoltaic agricultural greenhouse
Bright organic solar batteries and preparation method thereof and its application in photovoltaic agricultural greenhouse.
Background technology
Organic solar batteries have at low cost, light weight, flexibility, translucent, solution processable, are easy to large area preparation
The advantages that.Compared with inorganic material, organic extinction layer material has absorption spectrum discontinuous, and can be changed by changing its structure
The characteristics of becoming absorption spectrum, is easily formed in the translucent solar cell of visible light wave range.Currently, realizing translucent device simultaneously
Higher energy conversion efficiency and light transmittance are still faced with larger challenge.In recent years, non-fullerene acceptor material is due to having
Be readily synthesized, energy band easy-regulating and visible region or near-infrared region absorb the advantages that strong, cause the extensive concern of scientific research circle,
Currently, the efficiency of the single-unit organic solar batteries based on non-fullerene already exceed 13% (J.Am.Chem.Soc.2017,
139,7148).Further combined with the wider stronger absorption of non-fullerene acceptor material and the higher electricity of fullerene acceptor material
The advantages of transport factor, builds the organic solar batteries of ternary system, can be by the efficiency of single-unit organic solar batteries into one
Step is increased to 14% (Sci.Bull.2017,62,1562).Based on the non-fullerene for having absorption in infrared and near infrared band by
On the one hand the appearance of the efficient system of body material is conducive to the raising of translucent organic solar batteries performance, because of non-visible light
It can be absorbed and utilized by reflection and then by active layer；On the other hand translucent organic solar batteries can be pushed in building window or
The application of vehicle glass etc..In addition, photovoltaic agricultural greenhouse is also the potential important application of translucent organic solar batteries
One of field, however, there are no according to the selection of the absorption spectrum of green plants on how to being suitable for photovoltaic agriculture in document at present
The report of the organic material system of sparetime university's canopy.
Invention content
The primary purpose of the present invention is that providing a kind of translucent organic solar electricity can be applied to photovoltaic agricultural greenhouse
Pond.The active layer of the solar cell is to absorb stronger organic material in infrared and near infrared band.It is more as possible by making
Visible light-transmissive, non-visible light is absorbed and utilized by reflection and then by active layer, to improve the mean transmissivity of device simultaneously
And energy conversion efficiency.In addition, the main component in the transmitted spectrum and green plants of the translucent organic solar batteries
The absorption spectrum of chlorophyll matches.
Another object of the present invention is to provide the preparation methods of above-mentioned translucent organic solar batteries.
It is still another object of the present invention to provide the applications of above-mentioned translucent organic solar batteries.
The object of the invention is achieved through the following technical solutions：
A kind of translucent organic solar batteries, including stack gradually substrate, transparent anode, hole transmission layer, activity
Layer, electron transfer layer and transparent cathode；The active layer is to serve as small point of donor, non-fullerene based on organic polymer J52
Sub- IEICO-4F and fullerene PC71BM serves as the binary or ternary system of receptor, and the organic polymer J52, non-fullerene are small
Molecule IEICO-4F, fullerene PC71The mass ratio of BM is 1:(0~1.5):(0~1.5), the active layer thickness be 90~
100nm。
The organic polymer J52 is in document (Haijun Bin, etc.Non-Fullerene Polymer Solar
Cells Based on Alkylthio and Fluorine Substituted 2D-Conjugated Polymers
Reach 9.5%Efficiency [J] .Journal of the American Chemical Society.2016,138,
It is disclosed in 4657-4664), structural formula is：
Preferably, the hole transmission layer is PEDOT:PSS, thickness are 30~50nm.
The PEDOT:PSS Chineses are poly- 3,4-rthylene dioxythiophene/poly styrene sulfonate, are a kind of conductive high
Molecularly Imprinted Polymer.
Preferably, the electron transfer layer is PFN-Br, and thickness is 5~7nm.
Preferably, the substrate is glass.
Preferably, the transparent anode is ITO layer, is coated on substrate.
Preferably, the transparent cathode is Ag, and thickness is 10~100nm.
Preferably, the thickness of the active layer is 100nm, and the thickness of the transparent cathode is 15nm.
The absorption of main component chlorophyll in the transmitted spectrum and green plants of the translucent organic solar batteries
Spectral matching can be applied to photovoltaic agricultural greenhouse.
A kind of preparation method of translucent organic solar batteries, includes the following steps：
(1) glass substrate of the cleaning coated with ITO layer and drying；
(2) by PEDOT:PSS solution, which is spun in ITO layer, is used as hole transmission layer, and thickness is 30~50nm；Spin coating postposition
15~20min is made annealing treatment in 140~160 DEG C of warm tables；
(3) by donor material organic polymer J52, acceptor material IEICO-4F and PC71BM is mixed according to mass ratio
And be dissolved in solvent, it is configured to mixed solution；Then mixed solution is spun on PEDOT:On PSS hole transmission layers, thickness is obtained
Degree is the J52 of 90~100nm:IEICO-4F:PC71BM active layers；The organic polymer J52, non-fullerene small molecule
IEICO-4F, fullerene PC71The mass ratio of BM is 1:(0~1.5):(0~1.5)；
(4) PFN-Br solids are dissolved in methanol solvate, are configured to the solution of a concentration of 0.4~0.5mg/mL；Then will
Solution is spun on J52:IEICO-4F:PC71On BM active layers, the PFN-Br electron transfer layers that thickness is 5~7nm are formed；
(5) the Ag transparent cathodes that evaporation thickness is 10~100nm on PFN-Br electron transfer layers.
Preferably, the rotating speed of step (2) described spin coating is 3200~3500rpm.
Preferably, step (3) is described by donor material organic polymer J52, acceptor material IEICO-4F and PC71BM according to
Mass ratio carries out mixing and is dissolved in solvent, is configured to solution；Then mixed solution is spun on PEDOT:PSS hole transmission layers
On, specially：By donor material J52, acceptor material IEICO-4F and PC71BM is according to 1:(1.5~0):The quality of (0~1.5)
It is dissolved in 1,8- diiodo-octanes/chlorobenzene solvent that volume ratio is 0.5/99.5~1/99 than carrying out mixing, formation mixed solution, 50
~60 DEG C of 12~15h of stirring；Then mixed solution is spun on PEDOT:On PSS hole transmission layers, spin coating rate be 1000~
1200rpm。
Preferably, step (4) spin coating, specifically, spin coating rate is 2000~2200rpm.
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) present invention absorbs stronger non-fullerene acceptor using in infrared and near infrared band, by non-visible light quilt
The advantage for reflecting and then being absorbed and utilized by active layer, significantly improves the energy conversion efficiency of translucent organic solar batteries.
(2) present invention builds ternary system by introducing the higher fullerene acceptor of mobility, can further regulate and control semi-transparent
The energy conversion efficiency of funerary objects part and the relationship of mean transmissivity.
(3) the main component leaf in the transmitted spectrum and green plants of the translucent organic solar batteries in the present invention is green
The absorption spectrum of element etc. matches, and can be applied to photovoltaic agricultural greenhouse.
Description of the drawings
Fig. 1 is the translucent organic solar batteries active layer donor material J52, acceptor material of the embodiment of the present invention
IEICO-4F and PC71The abosrption spectrogram of BM films.
Fig. 2 is the schematic diagram of the translucent organic solar batteries device of the embodiment of the present invention.Wherein, 1 is substrate, 2
It is hole transmission layer for transparent anode, 3,4 be active layer, and 5 be electron transfer layer, and 6 be transparent cathode.
Fig. 3 is respectively 10,15 for silver electrode thickness in the translucent organic solar batteries device of the embodiment of the present invention 2
With transmitance distribution curve when 20nm.
Fig. 4 is the main component chlorophyll a and chlorophyll b in the green plants that the test of the embodiment of the present invention 2 obtains
Abosrption spectrogram.
Fig. 5 be the embodiment of the present invention 3 translucent organic solar batteries device in silver electrode thickness when being 15nm
Transmitance distribution curve.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) be coated with the glass substrate of ITO layer use successively acetone, micron level semiconductor special purpose detergent, deionized water,
Isopropanol is cleaned by ultrasonic, and drying nitrogen drying is placed in spare in culture dish；
(2) by PEDOT:PSS solution (being purchased from Heraeus companies), which is spun in ITO layer, is used as hole transmission layer, and rotating speed is
3200~3500rpm thickness is 40nm；Then 150 DEG C of thermal anneal process 15min；
(3) donor material J52 (being purchased from 1-Material companies) and acceptor material IEICO-4F is (public purchased from Solarmer
Department) and PC71BM (being purchased from Solenne B.V. companies) is respectively according to 1:(0~1.5)：The mass ratio of (0~1.5) is mixed,
It is dissolved in 1,8- diiodo-octanes/chlorobenzene solvent that volume ratio is 1/99, is configured to a concentration of 20mg mL-1Mixed solution, 55 DEG C
Stir 12h；Then mixed solution is spun on PEDOT:On PSS hole transmission layers, spin coating rate is 1000rpm, obtains thickness
For the active layer of 100nm；
(4) PFN-Br (being purchased from Solarmer companies) is dissolved in methanol solvate, is configured to a concentration of 0.5mg mL-1It is molten
Liquid is spun on J52:IEICO-4F:PC71On BM active layers, spin coating rate is 2200rpm, forms the electron-transport that thickness is 5nm
Layer；
(5) evaporation thickness is the silver electrode of 100nm as cathode on PFN-Br electron transfer layers.
Donor material J52 described in the present embodiment, acceptor material IEICO-4F and PC71Film absorption spectrum such as Fig. 1 institutes of BM
Show.IEICO-4F films have stronger absorption, ABSORPTION EDGE can be of about 970nm near infrared band.
The translucent organic solar batteries device architecture that the present embodiment obtains is as shown in Figure 2.
Photoelectric device performance test is carried out to the organic solar batteries of two-spot or ternary system described in embodiment 1, is visited
Difference PC in active layer is studied carefully71Influence of the BM contents to device performance, the results are shown in Table 1.
As shown in Table 1, by third component PC71The J52 that energy conversion efficiency is 9.21% is added in BM:IEICO-4F diploids
System, works as PC71When the content of BM is gradually increased to 40%, open-circuit voltage, short-circuit current density and fill factor are all improved, because
And the energy conversion efficiency of device shows the trend being gradually increased, and reaches as high as 10.68%；Work as PC71The content of BM increases to
When 60%, although short-circuit current density reduces, the energy conversion efficiency of ternary system remains above binary system.Illustrate triplet
System builds the performance for successfully improving device.
Table 1 is different to the/binary of acceptor ratio and the solar cell device performance indicator of ternary system
Embodiment 2
(1) be coated with the glass substrate of ITO layer use successively acetone, micron level semiconductor special purpose detergent, deionized water,
Isopropanol is cleaned by ultrasonic, and drying nitrogen drying is placed in spare in culture dish；
(2) by PEDOT:PSS solution (being purchased from Heraeus companies), which is spun in ITO layer, is used as hole transmission layer, and rotating speed is
3200~3500rpm, thickness are about 40nm；Then 150 DEG C of thermal anneal process 15min；
(3) donor material J52 (being purchased from 1-Material companies) and acceptor material IEICO-4F is (public purchased from Solarmer
Department) according to 1:1.5 mass ratio is mixed, and is dissolved in 1,8- diiodo-octanes/chlorobenzene solvent that volume ratio is 1/99, is configured to
A concentration of 20mg mL-1Mixed solution, 55 DEG C stirring 12h；Then mixed solution is spun on PEDOT:PSS hole transmission layers
On, spin coating rate is 1000rpm, obtains the active layer that thickness is 100nm；
(4) PFN-Br (being purchased from Solarmer companies) is dissolved in methanol solvate, is configured to a concentration of 0.5mg mL-1It is molten
Liquid is spun on J52:On IEICO-4F active layers, spin coating rate is 2200rpm, forms the electron transfer layer that thickness is 5nm；
(5) on PFN-Br electron transfer layers evaporation thickness be respectively 10,15 and 20nm silver-colored transparent cathode.
J52 in the present embodiment:The sun under the silver-colored transparent electrode thickness of difference of the translucent device of IEICO-4F binary systems
The results are shown in Table 2 for energy battery device performance parameter and light transmittance parameter testing.With the increase of silver electrode thickness, energy conversion
Efficiency gradually increases, and light transmittance continuously decreases.When silver electrode thickness is 15nm, mean transmissivity is up to 23.14%, at this time
It can get higher energy conversion efficiency (7.12%).
J52 in the present embodiment:The sun under the silver-colored transparent electrode thickness of difference of the translucent device of IEICO-4F binary systems
Energy battery device light transmittance distribution curve is as shown in Figure 3.Translucent device is saturating in 400~500nm and 600~700nm wave bands
Light rate is higher, this tests the absorption spectrum (as shown in Figure 4) of the main component chlorophyll in obtained green plants with us
Match, thus can be applied to photovoltaic agricultural greenhouse.
Solar cell device performance parameter under the different silver-colored transparent electrode thickness of table 2 and light transmittance parameter
Embodiment 3
(1) be coated with the glass substrate of ITO layer use successively acetone, micron level semiconductor special purpose detergent, deionized water,
Isopropanol is cleaned by ultrasonic, and drying nitrogen drying is placed in spare in culture dish；
(2) by PEDOT:PSS solution (being purchased from Heraeus companies), which is spun in ITO layer, is used as hole transmission layer, and rotating speed is
3200~3500rpm, thickness are about 40nm；Then 150 DEG C of thermal anneal process 15min.
(3) by donor material J52 (being purchased from 1-Material companies), acceptor material IEICO-4F is (public purchased from Solarmer
Department) and PC71BM (being purchased from Solenne B.V. companies) is respectively according to 1:0.9:0.6 mass ratio is mixed, and volume ratio is dissolved in
In 1,/99 1,8- diiodo-octanes/chlorobenzene solvent, to be configured to a concentration of 20mg mL-1Mixed solution, 55 DEG C stirring 12h；So
Mixed solution is spun on PEDOT afterwards:On PSS hole transmission layers, spin coating rate is 1000rpm, obtains the work that thickness is 100nm
Property layer；
(4) PFN-Br (being purchased from Solarmer companies) is dissolved in methanol solvate, is configured to a concentration of 0.5mg mL-1It is molten
Liquid is spun on J52:IEICO-4F:PC71On BM active layers, spin coating rate is 2200rpm, forms the electron-transport that thickness is 5nm
Layer；
(5) the silver-colored transparent cathode that evaporation thickness is 15nm on PFN-Br electron transfer layers.
J52 in the present embodiment:IEICO-4F:PC71The translucent device of BM ternary systems is 15nm in silver-colored transparent electrode thickness
When, device parameter performance and light transmittance parameter testing result are as follows：Open-circuit voltage 0.685V, short-circuit current density 16.90mA/
cm2, fill factor 66.9%, it is 7.75% that energy conversion efficiency, which is calculated, and average visible photopic light transmitance is 24.53%.With
Embodiment 2 is compared, and the energy conversion efficiency of translucent device is improved simultaneously with mean transmissivity.It is semi-transparent in the present embodiment
The light transmittance distribution curve of funerary objects part is as shown in figure 5, consistent with 2 curve peak position of embodiment, therefore superior performance in the present embodiment
Translucent organic solar batteries be more conducive to the application in photovoltaic agricultural greenhouse field.
By Examples 1 to 3 as it can be seen that the present invention by using infrared and near infrared band absorb stronger non-fullerene by
Body, and the higher fullerene acceptor structure ternary system of mobility is introduced, while improving the energy conversion effect of translucent device
Rate and mean transmissivity；Meanwhile it is main in the transmitted spectrum and green plants of translucent organic solar batteries of the invention
The absorption spectrum of ingredient chlorophyll matches, and can be applied to photovoltaic agricultural greenhouse.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of translucent organic solar batteries, including stack gradually substrate, transparent anode, hole transmission layer, active layer,
Electron transfer layer and transparent cathode, which is characterized in that the active layer is to serve as donor, non-fowler based on organic polymer 52
Alkene small molecule IEICO-4F and fullerene PC71BM serves as the binary or ternary system of receptor, the organic polymer J52, non-lipid
Strangle alkene small molecule IEICO-4F, fullerene PC71The mass ratio of BM is 1:(0~1.5):(0~1.5), the active layer thickness are
90~100nm.
2. a kind of translucent organic solar batteries according to claim 1, which is characterized in that the hole transmission layer is
PEDOT:PSS, thickness are 30~50nm.
3. a kind of translucent organic solar batteries according to claim 1, which is characterized in that the electron transfer layer is
PFN-Br, thickness are 5~7nm.
4. a kind of translucent organic solar batteries according to claim 1, which is characterized in that the substrate is glass.
5. a kind of translucent organic solar batteries according to claim 1, which is characterized in that the transparent anode is
ITO layer is coated on substrate.
6. a kind of translucent organic solar batteries according to claim 1, which is characterized in that the transparent cathode is
Ag, thickness are 10~100nm.
7. a kind of translucent organic solar batteries according to claim 1, which is characterized in that the thickness of the transparent cathode
Degree is 15nm；The thickness of the active layer is 100nm.
8. a kind of preparation method of translucent organic solar batteries, which is characterized in that include the following steps：
(1) glass substrate of the cleaning coated with ITO layer and drying；
(2) by PEDOT:PSS solution, which is spun in ITO layer, is used as hole transmission layer, and thickness is 30~50nm；Spin coating is placed on
140~160 DEG C of warm tables make annealing treatment 15~20min；
(3) by donor material organic polymer J52, acceptor material IEICO-4F and PC71BM according to mass ratio carry out mixing and it is molten
In solvent, it is configured to mixed solution；Then mixed solution is spun on PEDOT:On PSS hole transmission layers, obtaining thickness is
The J52 of 90~100nm:IEICO-4F:PC71BM active layers；The organic polymer J52, non-fullerene small molecule IEICO-4F,
Fullerene PC71The mass ratio of BM is 1:(0~1.5):(0~1.5)；
(4) PFN-Br solids are dissolved in methanol solvate, are configured to the solution of a concentration of 0.4~0.5mg/mL；Then by solution
It is spun on J52:IEICO-4F:PC71On BM active layers, the PFN-Br electron transfer layers that thickness is 5~7nm are formed；
(5) the Ag transparent cathodes that evaporation thickness is 10~100nm on PFN-Br electron transfer layers.
9. a kind of preparation method of translucent organic solar batteries according to claim 8, which is characterized in that step
(2) rate of the spin coating is 3200~3500rpm；
Step (3) described solvent is 1,8- diiodo-octanes/chlorobenzene solvent that volume ratio is 0.5/99.5~1/99；Spin coating rate is
1000~1200rpm；
The rate of step (4) described spin coating is 2000~2200rpm.
10. application of the translucent organic solar batteries described in claim 1 in photovoltaic agricultural greenhouse.
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| CN109817809A (en) * | 2019-01-14 | 2019-05-28 | 华南协同创新研究院 | A kind of ternary organic photovoltaic cell and preparation method thereof |
| CN111682110A (en) * | 2020-05-13 | 2020-09-18 | 华南理工大学 | Near infrared spectrum response polymer light detection device containing non-fullerene receptor |
| CN112420932A (en) * | 2020-11-19 | 2021-02-26 | 山东大学 | Organic photovoltaic device suitable for photoelectric conversion in indoor thermal light source illumination environment and preparation method thereof |
| CN112420932B (en) * | 2020-11-19 | 2023-07-04 | 山东大学 | Organic photovoltaic device suitable for photoelectric conversion under indoor thermal light source illumination environment and preparation method thereof |
| CN112928216A (en) * | 2021-02-03 | 2021-06-08 | 西湖大学 | Preparation method of high-transparency solar cell |
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